Treatment of wool-containing textile materials



umreo STATES PATENT OFFICE TREA T OF WOOL-CONTAINING TEXTILE MATERIALSLinton A. Flock, Jr., Plnckemin, N. 1., and John E. Lynn, Old Greenwich,and Eleanor L. MePhee, Stamford, Conn l-Isignors to American CyanamidCompany, New York, N. Y a corporation 01 Maine No Drawing. AppllcaflonAugust 1!, 194:, Serial No. 53,904

8 Claims. (GI. 8-1153) This invention relates to the treatment ortexsodium hypochlorite), alone or in the presence of tile materials, andmore particularly to the treatacidifying ents; alkalies (e. g., sodiumor potasment of wool and wool-containing fabric and sium hydroxide) ororganic bases, such agents other textile materials to impart improvedpropbeing used under conditions such that only the erties thereto,specifically increased resistance to 5 surface structure of the woolfibers is altered: shrinking. Still more particularly the inventionenzymes such as papain; and reducing agents is concerned with a processof reducing the such as sodium hydrogen sulfide and mercaptoshrinkingtendencies of a. wool-containing textile acetic (thioglycolic) acid.Another proposed material which comprises precondition ng the saidhrinkage-control proces has involved treating textile material by firsttreating it with an alkathe wool-containing textile with an aqueoussoluline solution, specifically an alkaline aqueous sotion of aheat-curable re which is thereafter lution or an alkaline organicsolvent (e. g.. an cured in situ, and then with a chlorine solution.alkaline alcoholic) solution, of a peroxy com- Still another suggestedproces has involved first pound (e. g., hydrogen peroxide, an organic ortreatng the woolen fabric with an alcoholic inorganic peroxide, aperhorate, a persulfate, etc.) caustic solution in such a manner thatthere is and thereafter removing the excess alkaline mano intrinsicdamage to the fibers and no harmful terial, e. g., by washing thepreconditioned texeffect on the hand of the fabric. In the second tile.The pretreated textile, with or without bestep of the process the woolenfabric is impreging dried, is then impregnated with an impregnated withan aqueous solution or dispersion of nant comprising a curable(polymerizable) catia heat-curable amino-aldehyde (e. g., ureaonicaminoplast, more particularly a colloidal soformaldehyde,melamine-formaldehyde, etc.) resiution (specifically an aqueouscolloidal solution) in-forming material or precondensate, after 01' acurable, cationic product of reaction of inwhich the impregnated fabricis heated to ingredients comprising an aminotrlazine. e. g., solubiiiaethe lmpregnant. (For a more complete melamine, and an aldehyde, e. g.,formaldehyde. description of this last-mentioned process, see Thecolloidal solutions or dispersions of cationic Pfeiler, Jr. et al.Patent No. 2,395,791 wherein aminopiasts used in practicing ourinvention are also are discussed the prior art processes deacidic, andthe glass electrode pH value thereof scribed briefly above and why they'are objecmay range, for example, between about 0.25 and tionable orfail completely to meet the requireabout 5 or 6, or even as high as 6.8,when the ments of a wool shrinkage-control agent or proccationicaminoplast (for instance, a partially ess.) polymerized, positivelycharged product of reac- It was also suggested prior to our inventiontion of ingredients comprising an aminotriazine, (see British Patent No.553,923) that wool-cone. g., melamine, and an aldehyde, e. g.,Iormaldetainlng textile materials be treated with an hyde) constitutes,on a net dr basis, about 6% aqueous alkaline solution (pH of 8 to 12) ofa by weight of the said solution. The cationic substance capable ofevolving oxygen (e. g., hyaminopiasts contained in the colloidalsolutions drogen peroxide, sodium peroxide, a persulfate, arehydrophilic, and their degree of polymerizaetc.) in order to reduce thetendency of the textlon is less than that which characterizes gels tileto felt and shrink. This treatment may be and precipitates which areundispersible by agiapplied to the textile either before or after it hastation with water but sufllcient to bring the been treated with asulfur-containing reducing particles thereof within the colloidal range.agent, e. g., sulfur dioxide, a sulfite, a bisulfite, a

Many different methods and agents have been hydrosulflte, etc. (seeBritish Patent No. 579,584)

used or suggested for use in the treatment of Another proposedshrinkage-control treatment fabrics and other textiles composed of orcon- 4 (see British Patent No. 564,958) has involved subtaining wool inorder to obviate or minimize their jecting the wool-containing textilematerial to a tendency to shrink on washing. The proposed mildchlorlnatlng o1- brominating treatment contreating agents have includedhalogens such as trolled at a pH of 4 and then to treatment withchlorine or bromine, solutions of sulfuryl chloanaqueous alkalinesolution of hydrogen peroxide. ride, hypochlorous acid, hpyochlorites(e. g., 59 Stillanother proposed method (see British Patent No. 569,730)of imparting shrinkage-resistance characteristics to wool-containingtextiles has involved treating the textile with an aqueous solution of apermanganate, e. g., potassium permanganate, and subsequently witheither an aqueous solution or suspension of a nitrogenchloro compound,e. g., nitrogen trichloride, monochloroamine, etc., or a dilute aqueoussolution of an alkaline hypochlorite or hypobromite.

A process which is now widely used to render woolen and wool-containingtextile materials resistant to shrinkage involves treating the textilewith an aqueous solution or dispersion of an alkylated, specificallymethylated, methyiol melamine, Iollowed by heating the impregnatedmaterial to cure the alkylated methylol melamine to a substantiallywater-insoluble condition. This method is described, for example, inJohnstone, Jr. et al. Reissue Patent No. 22,566.

It was also suggested prior to our invention that the fastness of dyedtextile material, specifically cotton, mercerized cotton, ramie, jute,hemp, sisal, silk, artificial silk and wool could be improved byimmersing the dyed material, immedi ately after the dyeing thereof, inan aqueous bath consisting of a solution of an aminotriazinealdehyderesin, more particularly a melaminetormaldehyde resin, in awater-soluble stage, which solution has been subjected to the action ofa strong mineral acid, specifically hydrochloric acid, for a period oftime suflicient to convert the resin into substantive state. The bathcontains the amount of resin which it is desired to apply to the textilematerial, and since the resin is substantive it is exhausted from thesolution and deposited on and between the fibers of the textilematerial. The final step of the process is the dryim of the wetimpregnated textile.

The present invention is based on our discovery that a wool-containingtextile material including wool itself in fabric or other form can berendered highly resistant to felting and shrinking by means of acationic aminoplast which is curable or polymerizable at normal or at anelevated temperature and which is applied in the form of 45 a colloidalsolution. more particularly an aqueous colloidal solution, provided thatthe woolcontaining textile is preconditioned as described briefly in thefirst paragraph of this specification prior to treatment with thecationic aminonlast, 50

which may be, for example, a cationic (positively charged) methylated orother alkvlated methylol melamine. The instant invention is separate andpatentablv distinct from that disclosed and claimed in the copendingapplication oi as Linton A. Fluck, Jr., John E. Lynn and Edward A.Schuman, Serial No. 43,963, filed concurrently herewith, and in whichlast-named application the'disclosed and claimed invention involves animprovement in a method of reducing the shrinking tendencies of awool-containing textile material with an aminoplast, more particularly anon-cationic aminoplast, adapted to effect this result, whichimprovement comprises treating the said textile material with analkaline solution of a peroxy compound, e. g., hydrogen peroxide, priorto treatment with the said non-cationic aminoplast.

It was wholly unobvious and unexpected that pretreating awool-containing textile with an alkaline solution of a peroxy compoundwould make it possible to use a cationic aminoplast as an agent forrendering such textiles highly shrink-resistant. and that. as a resultof such pretreatment, a substantially lesser amount of It the variouspersalts such an aminoplast can be employed as compared with a similaraminoplast which has not been rendered cationic and still obtain adesired degree 01' shrinkage resistance together with other advantagesdescribed below. The results are all the more surprising in view of ourfindings that the combination of treatments produces results quitediflerent from either treatment alone, as shown by examples whichfollow, and results which are not merely the sum of the individualtreatments.

Other advantages flowing from the peroxy pretreatment, and which a sowere quite surprising and in no way could have been predicted, includethe general uniformity in the results obtained with a given cationicaminoplast in treating a wider variety of textiles composed of orcontaining a proteinaceous material, specifically wool; and the abilityto impart shrink-resistant properties to woolen textiles whichheretofore could not be rendered resistant to shrinking to anappreciable Or a commercially satisfactory degree by previously knownmethods. Still another advantage accruing from our invention is that theapplied cationic aminoplast can be dried and cured or polymerized, as bya condensationpolymerization reaction, to its ultimate form (in whichform the cured or polymerized aminopiast is no longer dispersible inwater to form a colloidal solution or dispersion) at a much lowertemperature, for example at temperatures ranging from room temperature(65 F.- F.) to 225 F., as compared with the temperature required forsimilar aminoplasts which have not been rendered cationic, and stillimpart the same high order 0! shrink-resistant characteristics to thetreated textile. Since the use of lower curing or polymerizationtemperatures provides a material reduction in the cost of treating thetextile, it is immediately apparent that this advantage alone is ofgreat practical significance and commercial importance.

The reasons why the treatment of a wool-containing textile with analkaline solution of a peroxy compound prior to treatment with acationic methylated methylol melamine or other cationic aminoplast isabe to produce the valuable and unobvious results above described arenot understood. One possible explanation, which is supported by ourvisual observations, is that the treatment in some way alters thephysical and/ or chemical characteristics 0! the wool so that betterwetting and/or penetration occurs upon subsequent treatment with acationic aminoplast. This improvement in wettability and/orpenetrability is carried through any subsequent dyeing operation, asevidenced by the fact that no substantial differences in results areobtained when a dyeing step intervenes between the initialpreconditioning treatment of the undyed wool-containing textile and thefinal treatment of the textile with a cationic aminop'ast.

In carrying our invention into effect we first prepare an alkalinesolution. preferably an aqueous alkaline solution, of a peroxy compound,more particularly such a compound which, in an aqueous medium, yieldshydrogen peroxide or. ultimately, oxygen. Illustrative examples ofperoxy compounds that may be employed are hydrogen peroxide and otherinorganic peroxides (e. g., sodium, potassium and other alkali-metalperoxides), the organic peroxides (e. g., benzoyl peroxide, acetylperoxide, lauroyl peroxide, succinyl peroxide, tert-butyl hydroperoxide,etc.), including, for instance, the

8 alkali-metal (e. g., sodium, potassium, etc.), ammonium and otherperphosphates, persuli'ates, perborates, percarbonates, etc., thesepersalts in aqueous solutions forming hydrogen peroxide. Organicperacids (e. g., peracetic acid, perbenzoic acid. etc.) and thealkali-metal and ammonium salts of such acids also may be employed.Other percompounds which may be used include organic and organometallicsalts of hydrogen peroxide, for instance tetramethyl, tetraethyl andother tetralkyl ammonium peroxides, triethyl tin peroxide, etc.

The concentration of peroxy compound in the alkaline solution may bevaried widely depending, for example, upon the particularwool-containing textile employed, the particular peroxy compound used,the time and temperature of the treatment, etc. In general, however, theperoxy compound is used in an amount equivalent (oxidation equivalency)to at least about 0.05% by weight of hydrogen peroxide, based on theweight of the alkaline solution. Thus, when the peroxy compound ishydrogen peroxide, the alkaline pretreating solution ordinarily containsat least about 0.05%, more particularly at least about 0.1%, andpreferably at least about 0.2%, by weight of hydrogen perixide; or, ifthe peroxy compound charged to the bath is other than hydrogen peroxide,then an amount thereof which is chemically equivalent as an oxidizingagent to at least about 0.05%, more particularly at least about 0.1% andpreferably at least about 0.2%, by weight of hydrogen peroxide isemployed. In most cases optimum results have been obtained when theconcentration of the peroxy compound in the alkaline solution isequivalent to a hydrogen peroxide concentration of at least 0.3%, moreparticularly at least 0.5 or 0.6% by weight thereof. Higherconcentrations of peroxy compound, as for example concentrationsequivalent to hydrogen peroxide concentrations of the order of 2.5 or 3%or even 4 or 5% or more may be used if desired, but no particularadvantages appear to accrue therefrom. Due to its relatively low costand ease of handling the preferred peroxy compound is hydrogen peroxide,and generally it constitutes from about 0.3 to about 3%, moreparticularly from 0.5 to 2.5%, by weight of the alkaline solution, whichis preferably an aqueous alkaline solution. Although the preferredalkaline solution of the peroxy compound is an alkaline solution of thesaid compound in water, other alkaline solutions in which the peroxycompound is soluble may be employed such, for example, as alkalinesolutions of the peroxy compound in an alcohol (e. g., a monohydricalcohol such, for instance, as ethanol, propanol, butancl, etc.) or in amixture of water and an alcohol.

If the peroxy compound employed is of a kind which does not yield analkaline or a suiliciently alkaline treating bath, then the bath is madealkaline or is brought to a desired degree of alkalinity, as for examplea pH of from about 8 to about 12, and more particularly to a pH ofbetween 9 and 11, by the addition of an alkaline material or a materialwhich reacts alkaline in aqueous solution. Any material capable ofrendering the treating solution alkaline or of bringing the solution toa desired degree of alkalinity may be used, c. g., the sodium, potassiumand other alkali-metal hydroxides, acetates, carbonates andbicarbonates, ammonium hydroxide, amines (e. g., triethanolamine) borax,guanidine carbonate, disodium phosphate, sodium silicates,

0 soap, etc. Mixtures of substances which react basic in the aqueous orother solution of the peroxy compound may be used, if desired, forinstance mixtures of such substances as those just mentioned by way ofillustration.

The wool-containing textile to be preconditioned is treated with thealkaline solution of the peroxy compound in water or other solvent,preferably a volatile solvent, by any suitable method, for example byimmersing the textile in the solution. The treatment may be eflected bycontinuous, semhcontinuous or batch methods, or by combinations of suchmethods. For instance, a, wool-containing textile in skein, bolt orother form may be immersed in the treating solution for a periodsumcient to efl'ect the desired preconditioning treatment; or, thetextile in, for example, the form of a woven fabric may be continuouslypassed through a bath of the solution at a rate such that it is immersedin the bath for a. period suflicient to efl'ect the desired results. Ifnecessary, as for example when the wool-containing textile undergoingtreatment contains free acid, additional basic material may be added tothe pretreating bath during the treatment in order to maintain the bathat a desired pH value above 7.

The time of the treatment of the wool-containing textile with thepreconditioning solution may be varied considerably. Ordinarily,however, the contact time is at least 15 minutes, although in some caseseven shorter periods (for instance periods of the order of 5 or 10minutes) may be eifective. Better results generally are obtained whenthe textile is in intimate contact with the preconditioning solution fora period longer than 15 minutes, for example 30 minutes or longer. Thetime of contact may be 3 or 4 hours, or even as much as 1, 2 or moredays in some cases, depending, for example, upon the particularwool-containing textile which is being pretreated, the pH andtemperature of the treating solution, the kind and concentration ofperoxy compound therein, and other influencing factors. In most cases,however, no particular advantages appear to accrue when the contact timeis longer than about 30 minutes, such a contact time usually being aseilective as a contact time of minutes or even of 3 hours when the otherconditions including the peroxy compound (e. g., hydrogen peroxide),concentration thereof, alkaline material (e. g., sodium silicate), pH ofthe solution (e. g., about 10), temperature of the solution, etc., aremaintained substantially constant.

The temperature of the preconditioning solution also may be variedconsiderably but ordinarily it is within the range of about 110 F. toabout 160 F., the optimum temperature usually being about 125 F. In somecases, however, the solution temperature may be lower than 110 F., e.g., between or F. and F., or it may be higher than F., e. g., F. or F.

After treating the wool-containing textile with the alkaline solution(preferably an aqueous alkaline solution) of the peroxy compound, thetextile is water-washed and/or otherwise treated to remove the excessalkaline material. For example, the treated textile, after squeezing outthe excess liquid, may be merely water-washed to remove the excessalkali; or, it may be waterwashed and then rinsed in a dilute acidsolution (e.g., a 0.2 to 6 or 8% solution of a mineral acid such, forinstance as phosphoric acid or sulfuric acid. or a 0.2 to 10% solution01' an organic acid such, for example, as formic acid or acetic acid).after which the acid-rinsed textile is washed, e.g., with water, toremove the excess acid and water-soluble salts; or, the initial washingwith water may be omitted. and merely a dilute acid rinse followed by awater wash may be used. The cycle of rinsing in dilute acid followed bywater washing may be repeated numerous times, if necessary, in order toremove the excess alkaline material from the treated textile.

The preconditioning treatment herein described is applicable to bothundyed and dyed wool-containing textiles. When applied to dyedwoolcontainlng textiles there is usually some loss of dyestuif, butwhether or not this occurs depends, of course, upon the resistance ofthe particular dyestuif to the alkaline solution of the peroxy compound.

The preconditioned textile may be dyed by any of the methodsconventionally used in dyeing wool or wool-containing textiles withoutdetracting from the benefits of the peroxy pretreatment. For instance,wool in yarn, skein, fabric or other form may be dyed by top-chrome,meta-chrome or bottom-chrome dyeing methods. Typcal of such dyeingprocesses are those briefly described below:

Top-chrome dveina-The dyestufl is applied first to the cloth in aboiling bath. The bath is cooled, a chrome salt (usually sodium orpotassium dichromatel added, the bath brought to the boiling point, andthen boiled for from 30 to 45 minutes.

Meta-chrome dyeina.-The chrome salt and dyestufl are applied to the woolin the same bath. Dyeing is started cold and finished at the boil.

Bottom-chrome dyeiniL-Wool cloth is first boiled with a chromate in anacidified bath, the chrome color going onto the wool to give a darkgreen shade. The cloth is then boiled in a bath containing the dyestuil.The finished cloth may be any shade. Or, the wool may be dyed with ametallized dyestuif or an acid dyestull' such as are commonly used indyeing wool and in accordance with conventional practice. The wool alsomay be dyed with vat dyes.

The final operation in carrying our invention into effect is thetreatment of the preconditioned, dyed or undyed, wool-containing textilewith a curable (polymerizable) cationic aminoplast adapted to render thetextile resistant to shrinking when the said aminoplast has beensumciently cured (polymerized) at normal or at an elevated temperature,more particularly a colloidal solution (e.g., an aqueous colloidalsolution) of a curable (polymerizable) cationic product of reaction ofingredients comprising an aminotria-.

zine, e.g., melamine, ammeline, guanamine, acetoguanamine, etc., and analdehyde, e.g., formaldehyde. Also suitable for use in practicing ourinvention are curable, cationic products of reaction of ingredientscomprising (1) an aminotriazine, e.g., melamine. (2) urea, or analcohol, e.g., methanol, ethanol or other mcnohydric alcohol,or bothurea and an alcohol, and (3) an aldehyde, e.g., formaldehyde. Ordinarilywe use an aqueous colloidal solution of a partially polymerized,positively charged (cationic) product of reaction of ingredientscomprising melamine and formaldehyde, which solution has a glasselectrode pH value within the range of about 0.25 to about 4.0 when thesaid reaction product, on a net dry basis, constitutes about by weightof the said colloidal solution. In this colloidal solution the degree ofpolymerization of the aforementioned positively charged product ofreaction of ingredients comprising melamine and formaldehyde is lessthan that which characterizes gels and precipitates which areundispersible (that is, not permanently dispersible) by agitation withwater but is suflicient to bring the particles thereof within thecolloidal range. The colloidal solutions employed in the examples whichfollow have the aforementioned characteristics with respect to pH,degree of polymerisation of the reaction product contained therein, etc.

The colloidal solutions of curable. cationic aminoplasts used inpracticing our invention and the cationic aminoplastic themselves areprepared by known methods. Such methods are described in, for instance,wohnsiedler et al. Pat ents 2,345,543 and 2,356,718, Pollard Patents2,394,009, 2,417,014 and 2,423,428, and in the copending application ofHenry P. Wohnsiedler and Walter M. Thomas, Serial No. 516,932, filedJanuary 4, 1944, now Patent No. 2,485,079, and any of the cationicaminoplasts or colloidal solutions thereof disclosed (including thosewhich are claimed per se or are a part of the claimed subject matter) inthe aforementioned patents and application may be used in practicing ourinvention. Alkylated methylol melamines such as are disclosed inJohnstone. Jr. et al. Reissue Patent No. 22,566 may be renderedcolloidal by treatment with an acid in a manner such as is described inthe aforementioned wohnsiedler et a1. patents and applicat on and also.for example, in the aforementioned Pollard patents.

As is now known, certain aminoplasts including aminotriazine-aldehydecondensation products, when prepared in the presence of definitequantities of free acid (e. g., hydrochloric, phosphoric,pyrophosphoric, nitric, formic, acetic, chloroacetic, etc.) orsubsequently reacted with these same quantities of acid after theirpreparation by other methods, can be converted into colloidaldispersions wherein positive electrical charges are carried by thecolloidal particles of the resin. In this condition the resin solutionsor colloidal dispersions exhibit the property of migration of the resinparticles toward the cathode upon electrophoresis of the dispersion, andthis property characterizes all the aminoplast compositions employed inpracticing the present invention. (The cataphoresis is preferablycarried out by passing a direct current of -120 volts through platinumelectrodes immersed in the colloidal solution.) In general, suchaminoplast resins or condensation products, which may be designated morespecifically as acid-type" aminoplast resins or condensation products,and which include the acid-type aminotriazine-aldehyde condensationproducts, are readily identifled by the following characteristics:

(1) When freshly prepared they form clear solutions in both water andacids; and

(2) The clear solutions are converted upon aging first to hydrophiliccolloids, then to a waterdispersible gel stage, and finally upon dryingto a water-insoluble resin.

Other and more specific characteristics of colloidal aqueous solutionsof a partially polymerized, positively charged melamine-formaldehydecondensation product are disclosed and included in the claims of theaforementioned Wohnsiedler et al. Patent No. 2,345,543; andcharacteristics of colloidal aqueous solutions of a partiallypolymerized, positively charged suanamine-formala dehyde condensationproduct, in Wohnsiedler et al. Patent No. 2,856,718. As pointed out inthese patents, the iormation of a colloidal solution is shown in thefirst instance by the presence of a definite Tyndall efi'ect under theinfluence 01' a beam of light or in the dark field microscope. Althoughthe colloidal solution is infinitely dilutable with water it isextremely acid-sensitive, and this constitutes a very delicate test todetermine whether any colloidal acid-type resin is present. When astrong acid such as 6N hydrochloric acid is added to a clear, acidifiedresin solution that has not been aged noimmediate change occurs, butwhen the acid resin has been aged for a time sumcient to bring even asmall part of the resin particles within the colloidal range theseparticles are precipitated by the addition of the acid. This reactionwith strong acids can be used to estimate the degree oi polymerizationof the resin solution since the amount of acid necessary forprecipitation becomes less with increasing age of the solution.

Illustrative examples of other curable cationic aminoplasts that may beemployed in practicing the present invention are given, together withmethods of preparing such aminoplasts and colloidal solutions containingthe same, in the aforementioned Wohnsiedler et al. copending applicationSerial No. 516,932. The colloidal solutions disclosed and claimed inthis application may be described more particularly as being a colloidalaqueous solution of a resinous copolymer (or intercondensation product)of melamine, urea and formaldehyde, which copolymer contains at least0.7 mole of melamine for each 4 moles of urea and about 1 to 4 moles ofcombined formaldehyde for each mole of melamine plus urea and the saidcopolymer having a degree of polymerization such that the dispersedparticles thereof are colloidal in character and size. In such colloidalaqueous solutions a positive electric charge is carried by the dispersedcolloidal particles of the copolymer or intercondensation product asshown by their migration toward the cathode upon the passage of a directcurrent through the solution.

For a more complete understanding of the preparation of colloidalsolutions containing ourable cationic aminoplasts that may be used inpracticing our invention, reference is made to the above-mentionedWohnsiedler et al. copendi'ng application Serial No. 516,932 and theaforementioned Pollard Patents 2,394,009, 2,417,014 and 2,423,428 andWohnsiedler et al. Patents 2,345,543 and 2,356,718, the cationicaminoplast compositions therein disclosed (including those which areclaimed) being illustrative of those which can be employed in carryingthe present invention into effect.

The curable cationic aminoplast may be applied to the wool-containingtextile material in various ways. For example, if the cationicaminoplast is to be applied in the form of an aqueous colloidal solutioncontaining the same, the dry or substantially dry textile to be treatedmay be immersed in the aqueous colloidal solution containing particles01' cationic aminoplast of colloidal size, e. g., from, 0.01 to 1 micronin diameter, and then passed through pressure rolls, mangles orcentrifugal extractors to secure uniform impregnation and a controlledremoval of the excess material. The woolen fabric or otherwool-containing textile, however, also may be impregnated by othermethods, e. g., by spraying.

The liquid composition (e. g., an aqueous liquid r composition)containing the curable cationic aminoplast in the form of a colloid isdiluted with a suitable diluent or dispersion medium (e. g., water), iinecessary, to yield a finishing composition having the concentration ofsolids desired tor textile application. Thus, the concentration ofsolids in the liquid composition may be, for instance, from about 1 toabout 20% by weight of the composition depending, for example, upon theparticular diluent or mixture of diluents employed, method of expressionof the .1 wet, impregnated textile, etc. Ordinarily, however, thecurable cationic aminoplast constitutes from about 3 or 4% to about 10or 12% by weight of the liquid is. g., aqueous) finishing composition.The diluent or dispersion medium for the curable cationic aminoplast maybe varied depending, for example, upon the characteristics of the saidaminoplast, but in the case oi the preferred cationic aminoplasts it isusually water; or it may be, for instance, a mixture of water and analcohol, e. g., ethyl alcohol, glycerol, etc.

The pick-up oi the liquid (e. g., aqueous) finishing composition by thewool-containing textile material should be adjusted so that the finishedtextile contains an amount of cured aminoplast sui'ficient to impartshrinkresistant characteristics thereto which at least are adequate tomeet the minimum commercial requirements. This will vary somewhatdepending, for instance, upon the particular wool-containing textilebeing treated, the particular preconditioning treatment which has beengiven to it, the particular aminoplast employed, the particularproperties desired in the finished textile, etc. Ordinarily, however,the pick-up is adjusted so that the amount of aminoplast in the finishedtextile is not more than about (usually only about V: or less) as muchby weight as that required to obtain the same shrinkage-resistantcharacteristics in the absence of the preconditioning treatment. Forexample, the pick-up of the liquid finishing composition by thewoolcontaining textile material may be adjusted so that the finishedtextile contains from about 1 or 2% to about 6 or 8%. more particularlyfrom about 3% to about 5%, by weight of the dry textile, oi the cured(polymerized) aminoplast which, prior to curing is a curable(polymerizable) cationic (positively charged) aminoplast. In some cases,as for instance in the case of those woolen or wool-containing textileswhich normally are not amenable to treatment with a cationic aminoplastalone to yield a commercially satisfactory shrink-resistant textile, thepick-up oi the liquid finishing composition may be ad- Justed so thatthe finished textile contains as much as 10% or even about 15% or more,by weight of the dry textile, or the cured aminoplast. The amount ofaqueous or other liquid finishing composition picked up by the textile.that is. the so-called "wet pick-up, may be varied as desired or asconditions may require and may range, for examplepfrom about 30 or 40%up to about 150% or more by weight of the dry textile depending, forexample, upon the particular textile treated, method and conditions oftreatment, concentration of solids in the impregnating bath, amount ofsolids and properties desired in the finished textile, etc. When thewoolen fabric or other wool-containing textile material is impreghatedwith by weight of the dry textile, oi the textile-finishing composition,the impregnated textile will contain, after drying and ouring oi thecurable cationic aminoplast, nearly may be varied the same of curedaminoplast as the percentage oi curable cationic aminoplast which ispresent in the textile-finishing composition.

The wet. impregnated woolen fabric or other wool-containing textilematerial is then dried and cured. The drying and curing temperaturesconsiderably, but ordinarily temtherangeofaboutfib'or'id' F. up to about225 or 250 F. are employed. In some casesdryingand curingmaybeeifectahifdesired. at room temperature (65 l t-85 R). Thetlmeoidryingandcuringmaybeshortened by increasing the temperature, for exampleto temperatures of the order of 180 F. to 212 F.

peratures within 300 F. or 350 F.orcvenashighas400F.or more. As has beenpointed out hereinbeiore one of the main advantages accruing from theuse oi a curable cationic aminoplast as herein described is the lowerdrying and curing temperature that can be employed as compared with thetemperature required for similar aminoplasts which have not beenrendered cationic. and still impart the same high order ofshrink-resistant characteristics to the treated textile. In all casesthe dryingandcuringtemperatureandperiodaresufllcienttodrytheh'eatedtextileandtoadvance the cure or polymerizationof the curable or polymerizable cationic aminoplast contained thereinsubstantially beyond the stage which characterizes a gel, the cured orpolymerized amlnoplast being substantially water-insoluble and beingincapable of yielding a stable. aqueous colloidal solution ordispersion.

The drying and curing operation is flexible and may be varied to suitthe available equipment. Continuous methods are preferred.However,drying and curing also may be eflected by framing theimpregnated fabric to width, as on a pin tender, drying the framedfabric, batching it upon a shell and then aLowing it to stand at normalor at an elevated temperature for a period sufllcient to advance thecure or polymerization of the solid impregnant in situ to its ultimateform. In some cases drying and curing for from 2 hours to about 100hours at temperatures within the range of about 65 F. to about 200 F.may be required. Heating the dried fabrlc at higher temperatures rangingfrom a few seconds to a few minutes at highertemperatures of the orderof 212 F. to 250 F. or 300 F. or even as high as 400 F. or higher may beemployed, the shorter periods being used at the higher temperatures.

After the woolen fabric or other wool-containing textile material hasbeen treated as above described, it may be given a mild soapingtreatment to render it softer and more pliable. It then may be given theusual finishing treatments such as decatizing, brushing, shearing,pressing. etc. Our process may be applied to wool and wool-containing.textile materials, e. g., unwoven wool, yarns, worsteds, flannels,shirting, felts, knit or woven goods and others, and these may becomposed of all wool or partly of wool and partly of another fibrousmaterial, e. g., cotton. silk, any of the various rayons, any of thevarious other synthetic flbers inc.uding nylon, polyacrylonitrilefibers, fibers produced from casein, soya beans, etc.

In order that those skilled in the art better may understand how thepresent invention may be carried into eflect, the following examples aregiven by way oi illustration and not by way or and percentages are byExample 1 The textile material used in this example was 100% all wool,women's wear flannel weighing ll ounces per square yard. Pieces of thisflannel, 9 inches by 23 inches in size, and which had been suitablymarked for the purpose of measuring limitation. All parts weight.

shrinkage after washing, were treated as described below:

A. A sample of the flannel was immersed for 30 minutes in an aqueousalkaline solution containing 0.6% by weight of hydrogen peroxide andwhich had been rendered alkaline to a pH of about 10 with sodiumsilicate. The solution was maintained at a temperature of about 125 F.during the treating period. The treated flannel was removed from thebath, rinsed first in water. then in a dilute (about 1%) aqueoussolution oi acetic acid and again in water, squeezed through a padderand then dried on a frame, while holding it to its original size of 9inches by 23 inches, for about 6 to 10 minutes at about 225-2-i0 F.

8. Another sample oi the flannel was impregnated by immersing it for atleast about 1 minute in an aqueous colloidal solution containing about6% by weight of the acetic acid colloid of methylated methylol melamine,more particularly methylated trimethylol melamine. The solution alsocontained 0.01% of a, wetting agent, specifically a reaction product ofan ethanolamide of a long chain fatty acid and ethylene oxide. The wetflannel was then squeezed through a. padder to yield an impregnatedcloth in which the wet pick-up was about 100% by weight of the dryflannel. after which the sample was framed to size as in A, and thenheated for 10 minutes at 225 F. to dry the fabric and to advance thecure or polymerization of the colloidal methylated methylol melamine toa substantially completely cured or polymerized state, in which state itis substantially water-insoluble.

The acetic acid colloid of the methylated methylol melamine, moreparticularly methylated trimethylol melamine, was prepared as follows:

1 Parts Commercial methylated trimethylol melamine (about solids, waterconstituting most oi. the remainder) Water 883 Glacial acetic acid 42were mixed together and then allowed to stand undisturbed at roomtemperature (about B5- F.) for about 6 hours. The resulting aqueouscolloidal solution contained about 6% by weight of the acetic acidcolloid of methylated trimethylol melamine. The glass electrode pH valueof the aqueous colloidal solution was 3.3.

C. A sample of the flannel was preconditioned as described under A,followed by treatment as described under B.

D. Same as C with the exception that the wet impregnated flannel washeated for 9 minutes at 290 F. to dry the fabric and to advance the cureof the acetic acid colloid oi. methylated methylol melamine as describedunder B.

After cooling to room temperature each of the samples of A, B, C, and Dwas removed from the frame and given 10 washings (soapings) oi 10minutes each at F. in accordance with Federal Specifications CCC-T-l9la.After steam pressing and conditioning for about 16 hours at 70 F. and65% relative humidity, the samples were measured tor shrinkage in inchesper yard.

which values were then changed to percentages.Thewarpshnnkageinpercentcieachoi'the treated samples, together with thatof the untreated sample which had been similarly washed, are shownbelow. Other shrinkage values giveninotherexamplesweredeterminedinasimilar manner.

Thetextilematerialusedinthisexamplewas a Neolan dyed, 100% all woolflannel which weighed 8 ounces per square yard. It is typical of woolenfabrics which are less amenable to treatment with a methylated methylolmelamine alone or with an acetic acid colloid a methylated methylolmelamine than the flannel used in Example 1. The treatments were asfollows:

A. SameasA 0! Example 1. B. SameasBoiExample 1. C. BameasCol Example 1.D. sameascotltxampleiwiththeexception that the aqueous colloidalsolution oi the acetic acid colloid oi the methylated methylol melaminecontained about 2% (instead 0! about 6% as in 1-0) 01' the said colloid.

E. same as C of Example 1 with the exception that the aqueous colloidalsolution of the acetic acid colloid of the methylated methylol melaminecontained about 4% (instead of about 6% as in 1-0) of the said colloid.

The treated flannels and a control sample were washed as described underExample 1. The shrinkage data on the treated and washed sampics areshown below, together with tensile strength data on the untreated sampleand on the treated samples of A, B, and C.

Tensile fltrength in Warp Pounds Treatment Shrinkage inPerCent WarpFilling no 33.0 I10 trample 3 This example illustrates the resultsobtained when various temperature conditions are used in drying andcuring the impregnated woolen textile. The woolen goods employed was aNeolan dyed woolen flannel such as was used in Example 2. The treatmentswere as follows:

14 thatthedyedi'abriaatterbeingimpreansted with the aqueous colloidalsolution containim about 6% by weight oi. the acetic acid colloid oi'methylated methylol melamine, was dried and cured at room temperature(about 65'-85 1".) for about 18 hours.

B. Same as C of Example 1 wherein the impregnated textile was dried andcured for 10 minutes at 225' I C. sameascoinxamplelwiththeexcepticn thatthe temperature at which the imp snated2utiiewasdriedandcuredifavrlliminuteswas D.samesscoinxamplelwiththeexceptionthattheimpregnatedtextilewasdriedandcured for 9 minutm at 290' I".

'lhe treated tunnels and a control sample were washed as described underExample 1. The shrinkage data on the treated and washed samples areshown 'below:

Treatment been:

Emple This example illustrate the diii'erences in the curing ofpolymerization conditions that can be used and the results obtained whena peroxide pretreated wool-containing textile is treated with anordinary aqueous solution of a methylated methylol melamine and withaqueous colloidal solutions oi an acid colloid, more particularly anacetic acid colloid, of the same methylated methylol melamine. Thetextile was an undyed womenswear liannel, all wool. weighing 8 ouncesper square yard. The treatments were as follows:

A. A sample of the flannel was preconditioned by treatment with anaqueous alkaline solution of hydrogen peroxide as described under A oiExample 1. The preconditioned fabric was impresnated by immersing it forabout 1 minute in an aqueous solution containing about 5% by weight ofmethylated methylol melamine, more particularly methylated trimethylolmelamine. The solution also contained, by weight, 0.155% of a curingcatalyst. specifically diammonium hydrogen phosphate, and 0.03% o! awetting agent, specifically dioctyl sodium sulfosuccinate. The wetflannel was then squeezed through a padder to yield an impregnated clothin which the wet pick-up was about 100% by weight oi the dry. flannel,after which the sample was framed to size as in l-A, and then heated for10 minutes at 225 F. to dry the fabric and to advance the cure oi themethylated methylol melamine as described under l-B.

Another sample was treated as above described with the exception thatthe impregnated flannel was heated for 9 minutes at 290 F.

B. Same as A oi this example with the exception that the preconditionedflannel was impregnated with an aqueous colloidal solution of an aceticacid colloid of the same methylated methyl- A. sameascoi Examplelwiththeexception 5 olmelamineusedinA;als0,thcaqueollscollddll 15solution contained about 4% by weight of the said colloid instead ofabout 5% of solids as in A of this example, and 0.01% 01' a non-ionicwetting agent, more particularly a reaction product of an ethanolamideof a long chain fatty acid and ethylene oxide. The wet impregnatedtextile was heated for minutes at 225 F. as described in the firstparagraph of A oi the present example.

Other samples were treated as above described with the exception thateach 01' the impregnated fabrics was heated under different conditions,via, 10 minutes at 250 F. and 275 F., and 9 minutes at 290 F.

C. Same as]; with the exception that samples of the woolen flannel wereimpregnated with the same acetic acid colloid in a concentration 0!about 6% by weight or the aqueous colloidal solution instead of about4%. Each oi the impregnated flannels was heated under diil'erentconditions. vlz., 30 minutes at 180 F.. 10 minutes at 225 F. and 9minutes at 290 F.

The treated fiannels and a control sample were washed as described underExample 1. The shrinkage data on the treated and washed samples areshown below:

Warp Shrinkage in Per Cent, Sample Dried and Cured atwhen undyedwool-containing textile materials are to be rendered resistant toshrinking in accordance with our invention, a preferred preconditioningtreatment includes the step of rinsing the peroxy pretreated textilewith a dilute acid solution as hereinbeiore described, followed by awater rinse. Under the usual conditions prevailing in a textile millwherein the acid colloid is applied to a dyed textile, such an acidrinse is unnecessary since the wool is generally dyed in an acid (e. g.,sulfuric or acetic acid) medium.

The following example illustrates the results obtained using a peroxypretreating operation wherein, in one case, the peroxy-pretreated fabricwas rinsed in a dilute acid solution and, in another case, the acidrinse was omitted.

Example 5 Varp Shrinkage Treatment in Per Cent It is not necessary thatthe wool-containing textile material be dried after completion oi thealkaline peroxy pretreatment. In other words the pretreated, washed andsqueezed, impregnated textile may be treated while still wet with theaqueous colloidal solution oi the acid colloid. This is shown by thefollowing example.

Example 6 The textile material used in this was a dyed woolen flannelsuch as was used in Example 2. The treatments were as follows:

A. Same as D of Example 2 with the exception that the woolen fabric,after treatment with the aqueous alkaline solution containing 0.6% byweight oi hydrogen peroxide and subsequent rinsing as therein described,was immersed directly, without being dried, in the aqueous colloidalsolution containing about 2% by weight of the acetlcacid colloid oimethylated methylol melamine.

B. Same as A of this example with the exception that the aqueouscolloidal solution contained about 4% by weight of the actetic acidcolloid.

C. Same as A of this example with the'exception that the aqueouscolloidal solution contained about 6% by weight of the acetic acidcolloid.

The treated fiannels and a control sample were washed as described underExample 1. The shrinkage data on the treated and washed samples areshown below:

wargshrlnkage None A It will be noted that the shrink-resistantproperties of the treated flannels are of the same order as those of thetreated fabrics or C, D, and E 0! Example 2.

Example 7 This example illustrates the preparation and use, inaccordance with our invention, of an aqueous colloidal solutioncontaining a hydrochloric acid colloid of methylated methylol melamine,more particularly methylated trimethylol melamine.

A x. Parts 1581?, Ratio Commercial methylated trimethylol melamine gboutm soiids, water constituting most of e Aquarius hydrochloric acid (about38% HCl)-.- Water 17 textile material resistant to shrinking asdescribed below. The woolen material was a women's wear flannel such asused in Example 1.

A. Same a C of Example 1 with the exception that the above-describedaqueous colloidal solution containing the hydrochloric acid colloid ofmethylated trimethylol melaminewas used instead of the correspondingacetic acid colloid. The wet, impregnated fabric was dried and cured for10 minutes at 225 F. Another alkaline hydrogen peroxide pretreatedsample (B) was dried and cured for 30 minutes at 180 F., while a third,similarly pretreated sample (C) was dried and cured for 9 minutes at 290F.

The treated samples and a control sample were washed as described underExample 1. The shrinkage data on the treated and washed samplw are shownbelow, together with tensile strength data on the untreated sample andon the This example illustrates the preparation and use, in accordancewith our invention, of an aqueous colloidal solution containing aphosphoric acid colloid of methylated methylol melamine, moreparticularly methylated trimethylol melamine.

Approx. Parts Molar Ratio Commercial meth lated trimetb lol melamine(about 80% soil water const tuted most of the remainder) 25 1.Phosphoric acid (85% H:P0|) l3 1. 4 Water- 102 were mixed together andthen allowed to stand undisturbed at room temperature (about 65 F.- 85F.) for about hours. The resulting aqueous colloidal solution containedabout 10% of solids, which thereafter was diluted with water to asolution containing about 6% of solids, and used as described in thepreceding example instead of the hydrochloric acid colloid of thatexample. The glass electrode pH value of the aqueous colloidal solutioncontaining 6% solids was 1.5. One wet, impregnated sample (A) was driedand cured for 10 minutes at 225" F., while another sample (B) was driedand cured for 9 minutes at 290 F. After being washed ten times asdescribed under Example 1, the warp shrinkage in percent of each of thetreated samples was 4.7. The warp shrinkage in per cent of a control(untreated) sample, after having been similarly washed ten times, was20.0.

Example 9 This example illustrates the preparation and use, inaccordance with our invention, of an aqueous colloidal solutioncontaining a hydrochlo ric acid colloid of a melamine-formaldehydereaction product, more particularly trlmethyiol melamine.

were mixed together and then allowed to stand undisturbed at roomtemperature (about 65- F.) for about 8 hours. The resulting aqueouscolloidal solution contained about 11.5% of solids. One part was dilutedwith water to yield a colloidal solution, (A) containing about 2% of ahydrochloric acid colloid of trimethylol melamine. Similarly, water wasadded to another part to form a colloidal solution (B) containing about4% of the said colloid. Both solutions were applied to an alkalinehydrogen peroxide preconditioned woolen fabric as described underExample 8. The wet, impregnated fabrics were dried and cured for 9minutes at 290 F. After bein washed ten times as described under Example1, the warp shrinkage in per cent of the fabric which had been treatedwith the colloidal solution (A) containin 2% of the colloid was 4.2,while that of the fabric which had been treated with the colloidalsolution (B) containing 4% of the colloid was 5.6. The warp shrinkage inper cent of a control sample, after having been similarly washed tentimes, was 20.0.

Example 10 The process of our invention is applicable to a wide varietyof woolen textile materials, as shown by the following results oftreating six different woolen fabrics. The treatments were as follows:

A. Same as C of Example 1.

B. Same as D of Example 1.

(The treatments of A and B involved a pretreatment of the fabrics withan aqueous alkaline solution containing 0.6% hydrogen peroxide and afinishing treatment with an aqueous colloidal solution containing about6% of the acetic acid colloid of methylated trimethylol melamine. In theA treatment the wet, impregnated textile was dried and cured for 10minutes at 225 F., while in the B treatment it was dried and cured for 9minutes at 290 F.) The warp shrinkage in per cent of the untreated andtreated fabrics, after being washed ten times as described under Example1, are shown below:

Warp Shrinkage in Per Cent oi Woolen Fabrics was doses:

Nora-Fabrics l, 2 and 3 were undyed women's wear flannel, all wool,weighing 8 ounces per square yard. Fabrics 4 and 5 were Palatine dyedand top-chrome dyed, respectively, sulfuric acid carbonized woolenfabrics (100% all wool weighing about 12 ounces for square yard, whileFabr c 6 was an undfed, all wool, sulfuric acid carbonized fabric whichalso we ghed about 12 ounces per square yard.

Optimum results in practicing our invention are obtained by using aperoxy pretreating so- 19 lution which not only is distinctly alkalinewhen the wool-containing textile material initially is immersed thereinbut which is maintained alkaline during the entire period the woolenmaterial is in the pretreatin bath. This is shown by the followingexample.

Example 11 The general method of treatment was the same as describedunder C of Example 1.

The woolen fabrics treated in A and B were sulfuric acid carbonizedwoolen materials and contained excess sulfuric acid. In A the pH of thepretreating solution was not controlled. while in B additional sodiumsilicate was added to the hydrogen peroxide pretreating solution duringthe treating period so that the pH of the solution did not fall below 9.

Example 12 The woolen fabric which was treated in this example was aNeolan dyed, 100% all wool flannel which weighed 8 ounces per squareyard. Instead of using hydrogen peroxide in the pretreating bath as inthe previous examples, a different peroxy compound, via, sodiumperborate, was employed. The treatments were as follows:

A. The woolen fabric was preconditioned by immersing it in an aqueousalkaline solution containing 1% by weight of sodium perbo'rate. Nosodium silicate was added to the bath since the sodium perborate alonebrought the bath to a pH of about 10. The flannel was allowed to remainin the bath for 30 minutes while maintaining, the solution at 125 F. Thetreated flannel was removed from the bath. rinsed in water to remove theexcess alkali, squeezed through a padder and then dried on a frame,while holding it to its original size of 9 inches by 23 inches, for 10minutes at 240 F. The dried flannel was impregnated by immersing it forat least about 1 minute in a textile-finishing composition comprising anaqueous solution containing about 5% by weight of methylated methylolmelamine, more particularly methylated trimethylol melamine. Thesolution also contained, by weight, 0.155% of a curing catalyst,specifically diammoniu-m hydrogen phosphate, and 0.03% of a wettingagent, specificaliy dioctyl sodium sulfosuccinate. The wet flannel wasthen squeezed and framed as described under B of Example 1, after whichit was heated for 9 minutes at 290 F. to dry the fabric and to advancethe cure of the methylated methylol melamine as described under 113.

B. Same as A of this example with the exception that thetextile-finishing composition comprised an aqueous colloidal solutioncontaining 5% of an acetic acid colloid (prepared in a manner similar tothat described under 1-3) of methylated trimethylol melamine. Thesolution contained no added curing catalyst, but did contain 0.01% of anon-ionic wetting agent, more particularly a reaction product of anethanolamide of a long chain fatty acid and ethylene oxide.

The treated flannels and a control sample (un treated flannel) weresubjected to washing in soap solution, more particularly five washingcycles of 10 minutes each followed by drying, and then were washed for 1hour followed by drying. The data on shrinkage of the treated and washedsamples are shown below:

Treatment Example 13 The woolen fabric treated in this example was awomens wear flannel such as was used in Example 1. The treatments wereas follows:

A. The flannel, without any preconditioning treatment, was treated withan aqueous colloidal solution containing 5% of the acetic acid colloidof methylated trimethylol melamine and 0.01% of a non-ionic wettingagent as described under A of Example 12.

B. Same as A or this example with the exception that the aqueouscolloidal solution contained 10% of the acetic acid colloid.

C. Same as B of Example 12 with the exception that the aqueous alkalinepretreating solution contained 0.6% hydrogen peroxide and had beenrendered alkaline to a pH of about lo with sodium silicate. Thetextile-finishing composition comprised an aqueous colloidal solutioncontaining 5% by weight thereof of an acetic acid colloid of methylatedtrimethylol melamine.

D. Same as C of this example with the exception that the aqueouscolloidal solution contained 10% of the acetic acid colloid ofmethylated trimethylol melamine.

The treated flannels and a. control sample were washed as describedunder Example 12. The data on shrinkage of the treated and washedsamples are shown below:

Warp Shrinkage in Per Cent Alter 5 Washin; O 0123 of 10 M utes Each ofAdditional Washing Example 14 The same woolen fabric was treated as wasused in Example 13. The treatments were as follows:

A. Same as A of Example 12 with the exception that the aqueous alkalinepretreating solution contained 0.6% hydrogen peroxide and had beenrendered alkaline to a pH of about 10 with sodium silicate; also, thetextile finishing composition comprised an aqueous solution containingonly about 2 /2% of methylated trimethylol melamine, about 0.08% ofdiammonium hydrogen phosphate and about 0.03% of dioctyl sodiumsulfosuccinate as a wetting agent.

B. The pretreating solution and method were the same as A of thisexample, while the finishing treatment also was the same with theexception that the textile finishing composition contained 2i 2%% of anacetic acid colloid of methylated trimethylol melamine (see 1-8 formethod of preparation) and the same kind and amount of wetting agent asdescribed under B of Example 12.

The treated samples and a control sample were washed as described underExample 12. The shrinkage data on the treated and washed samples areshown below:

3 Warp Treatment B Cent 1 None.. 21.1 A ll. 8 B 3. 3

I After 6 Washing Cycles of 10 Minutes Each Followed by 1 Hour ofAdditional Washing.

Example A. Same as A of Example 12 with the exception that the aqueousalkaline pretreating solution contained 0.6% hydrogen peroxide and hadbeen rendered alkaline to a pH of about 10 with sodium silicate; also,the preconditioning bath was maintained at a temperature of 100' l". for8 hours instead of at 125 F. for minutes as in l2-A. Thetextile-finishing composition contained about 5% by weight of methylatedtrimethylol melamine and the same kind and amount of curing catalyst andwetting agent as in 12-A.

B. Same as A of this example with the exception that thetextile-finishing composition comprised an aqueous colloidal solutioncontaining 6% of an acetic acid colloid (prepared in a manner similar tothat described under 1-3) of methylated trimethylol melamine. Thesolution also contained 0.01% of a non-ionic wetting agent such asdescribed under 143.

C. Same as A of this example with the exception that the alkalinehydrogen peroxide pretreating bath was maintained at a temperature ofabout 80 F. for about 24 hours.

D. Same as B of this example with the exception that the preconditioningsolution was maintained at about 80 F. for about 24 hours.

The treated flannels and a control sample were washed as described underExample 12. The shrinkage data on the treated and washed samples areshown below:

I After 6 Washing Cycles of 10 Minutes Each Followed by 1 Hour ofAdditional Washing.

Example 16 This example illustrates the use of other peroxy compounds,specifically sodium peroxide and potassium persulfate, as components ofthe pre- 22 conditioning bath. The woolen fabric was thesameasthatusedinExample 1. Thetreatmente were as follows:

A. Same as D of Example 1 with the exception that the pretreating bathcontained bi: by weight of sodium peroxide. The sodium peroxide alonebrought the solution to a pH of about 10 and no other alkaline materialwas added.

B. Same as D of Example 1 with the exception that the preconditioningsolution contained 1% by weight of potassium persulfate. Sodium silicatewas added in an amount sumcient to bring the pretreating bath to a pH ofabout 10.

The treated flannels and a control sample were washed as described underExample 12. The shrinkage data on the treated and washed sampics areshown below:

The textile material used in this example was all wool, undyed women'swear flannel similar to that used in Example 1. The treatments were asfollows:

A. Same as C of Example 1, which involved pretreatment of the fabricwith an aqueous alkaline solution containing 0.8% by weight of hydrogenperoxide and rendered alkaline with sodium silicate to a pH of about 10,and subsequent treatment of the dried, undyed fabric with an aqueouscolloidal solution containing 6% by weight of an acid colloid ofmethylated trimethylol melamine.

B. Same as A of this example with the exception that afterpreconditioning the undyed fabric as in A but omitting the acetic acidrinse. it was dyed as follows: The dried, pretreated cloth was immersedfor 1 hour in a dye bath maintained at boiling temperature andcontaining 3% of a dye (Calcocid Violet 4 Bx, Color Index No. 698) 4% ofacetic acid (approx. 28% CHsCOOH) and 7% of Glaubers salt, thepercentages of dye, acetic acid and Glaubers salt being by weight andbeing based on the weight of the dry fabric. After rinsing the dyedtextile in water, followed by drying, the dyed and dried fabric wastreated with an aqueous colloidal solution containing 6% by weight of anacetic acid colloid of methylated trimethylol melamine as in A of thisexample.

The treated ilannels were washed as described under Example 1, with theexception that each was given only 5 washings of 10 minutes each. Theshrinkage data on the treated and washed After 5 Washing Cycles of 10Minutes Eseb.

It will be understood, of course. by those skilled in the art that ourinvention is not limited to the particular preconditioning compositions,curable cationic aminoplasts and conditions of treating awool-containing textile with these compositions as has been given by wayof illustration in the above examples, since the pretreating solution,the ilnal textile-finishing composition and the application conditionsmay be widely varied as will be apparent from the description in thisspecification prior to the examples.

The terms textile" and textile material as used gen rally herein and inthe appended claims include within their meanings filaments, fibers.rovings, slivers, threads, yarns, twisted yarns, etc., as such or inwoven felted or otherwise formed fabrics, sheets, cloths and the like.

We claim:

1. A process of reducing the shrinking tendencies of a wool-containingtextile material which comprises preconditioning the said textilematerial by first treating it with an alkaline solution of a peroxycompound and thereafter removing the excess alkaline material,impregnating the preconditioned textile with an impregnant comprising acolloidal solution of a curable cationic aminoplast, and advancing thecure of the said aminoplast in situ, the amount of the cured aminoplastwith which the said textile material i impregnated being suiilcient torender it resistant to shrinking.

2. A process as in claim 1 wherein the alkaline solution of the peroxycompound is within a pH range of 8 to 12.

ii. A process as in claim 1 wherein the impregnant comprises a colloidalsolution of a curable, cationic product of reaction of ingredientscomprising melamine and formaldehyde.

4. A process of reducing the shrinking tendencies of a dyed woolenfabric which comprises preconditioning the undyed fabric by firsttreating it with an aqueous alkaline solution of hydrogen peroxide andthereafter removing the excess alkaline material, dyeing thepreconditioned fabric, impregnating the dyed fabric with an aqueouscolloidal solution of a partially polymerized, positively chargedproduct of reaction of ingredients comprising melamine and formaldehyde,said colloidal solution having a glass electrode pH value within therange of 0.25 to 6.8 when the said reaction product, on a net dry basis,constitutes about 6% by weight of the said colloidal solution, and thedegree of polymerization of the said reaction product being less thanthat which characterizes gels and precipitates which are undispersibleby agitation with water but suiilcient to bring the particles thereofwithin the colloidal range, and polymerizing the said reaction productin situ to its ultimate form, the polymerized reaction product beingsubstantially water-insoluble, and the amount or the said reactionproduct in polymerized state with which the fabric is impregnated beingfrom 1 to by weight of the dry fabric.

5. A process oi. reducing the shrinking tendencies of a dyed,wool-containing textile which comprises immersing the undyed textile inan aqueous solution rendered alkaline to a pH of between 8 and 12 andcontaining hydrogen peroxide in an amount corresponding to from 0.05% to3% by weight of the said solution and thereafter removing the excessalkaline material thereby to precondition the undyed textile, dyeing thepreconditioned textile, impregnating the 24 dyed textile with an aqueouscolloidal solution of a partially polymerized, positively chargedalkylated methylol melamine, said colloidal solution having a glasselectrode pH value within the range or about 0.25 to about 4.0 when thesaid alkylated methylol melamine, on a net dry basis, constitutes about6% by weight of the said colloldal solution, and the degree ofpolymerization oi the said alkylated methylol melamine being less thanthat which characterizes gels and precipitates which are undispersibleby agitation with water but suiilcient to bring the particles thereofwithin the colloidal range, drying the wet imnregnated textile andpolymerizing the said alkylated methylol melamine contained in theimpregnated textile to its ultimate degree of polymerization, saiddrying and polymerization being efiected at a temperature not exceeding400 F., and the amount of the said alkylated methylol melamine inpolymerized state with which the textile is impregnated being from 1 to15% by weight of the dry textile.

6. A process as in claim 5 wherein the colloidal solution containsmethylated methylol melamine rendered colloidal with acetic acid.

7. A process as in claim 5 wherein the alkylated methylol melamine ismethylated methylol melamine, and the wet impregnated textile is driedand the methylated methylol melamine contained in the impregnatedtextile is polymerized to its ultimate degree of polymerization at atemperature within the range of about 65 F. to about 300 F.

8. The method of reducing the shrinking tendencies of a woolen textilematerial which comprises immersing the said material in undyed statei'or from Y; to 3 hours in an aqueous solu-,

tion rendered alkaline to a pH of between 9 and 11 and containinghydrogen peroxide in an amount corresponding to from 0.5 to 2.5% byweight of the said solution thereby to precondition the said textilematerial, said solution being maintained at a temperature of from 70 F.to F.; removing the excess alkaline material from the preconditionedtextile; impregnating the preconditioned textile from which the excessalkaline material has been removed with an aqueous colloidal solution ofa partially polymerized, positively charged methylated methylol melaminerendered colloidal with acetic acid, said solution containing from about2% to about 12% by weight of the said methylated methylol melamine andhaving a glass electrode pH value within the range of about 0.25 toabout 4.0 when the said methylated methylol melamine, on a net drybasis, constitutes about 6% by weight of the said colloidal solution,and the degree of polymerization of the said methylated methylolmelamine being less than that which characterizes gels and precipitateswhich are undispersible by agitation with water but suiilcient to bringthe particles thereof within the colloidal range; adjusting the pick-upof the said aqueous colloidal solution by the said preconditionedtextile so that the amount of cured methylated methylol melamine in thefinished textile is not more than about three-fourths as much by weightas that required to obtain the same shrinkprooiing characteristics inthe absence of the aforedescribed preconditioning treatment; drying thewet impregnated textile and polymerizing the said methylated methylolmelamine contained in the impregnated textile to its ultimate degree oipolymerization, said drying and polymerization 25 29 being eflected at atemperature within the range Number Name me of about 65 F. to about 225F. 2,329,651 Powers Sept. 14, 1943 LBTION A. FLUCK, JR. 2,395,724 CowleyFeb. 28, 1946 JOHN E. LYNN. 2,395,791 Ptetl'er Feb. 28, 1948 ELEANOR L.MCPHE'E. 5 2,423,429 Pollard July 1, I947 REFERENCES CIT D 2.467.293Rust Apr. 12, 1949 The following references are of record In the FOREIGNPA H 8 me or this mm: 10 33305 o 1 3 121 A 2519 rea r n pr. UmDNmAm553,923 Great Britain 1943 Number lime be assen Schweitzer Aug. 30, 1921OTHER mm 2,070,210 Mason Feb- 9, 1937 Matthews: Bleaching and RelatedProcesses, 2,107,297 Kaufl'mann Feb. 0, 1939 15 Chemical Catalog Co.,New York, 1921, pages 2,238,949 Schlack Apr- 1941 187-145. (Book inDivision 48;) 2,329,622 Johnsfone flept. 14, 1943

1. A PROCESS OF REDUCING THE SHRINKING TENDENCES OF A WOOL-CONTAININGTEXTILE MATERIAL WHICH COMPRISES PRECONDITIONING THE SAID TEXTILEMATERIAL BY FIRST TREATING IT WITH AN ALKALINE SOLUTION OF A PEROXYCOMPOUND AND THEREAFTER REMOVING THE EXCESS ALKALINE MATERIAL,IMPREGNATING THE PRECONDITIONED TEXTILE WITH AN IMPREGNANT COMPRISING ACOLLOIDAL SOLUTION OF A CURABLE CATIONIC AMINOPLAST, AND ADVANCING THECURE OF THE SAID AMINOPLAST IN SITU, THE AMOUNT OF THE CURED AMINOPLASTWITH WHICH THE SAID TEXTILE MATERIAL IS IMPREGNATED BEING SUFFICIENT TORENDER IT RESISTANT TO SHRINKING.